EP0144039B1 - Preminarily foamed particles of non-crosslinked polypropylenetype resin - Google Patents

Preminarily foamed particles of non-crosslinked polypropylenetype resin Download PDF

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Publication number
EP0144039B1
EP0144039B1 EP84114032A EP84114032A EP0144039B1 EP 0144039 B1 EP0144039 B1 EP 0144039B1 EP 84114032 A EP84114032 A EP 84114032A EP 84114032 A EP84114032 A EP 84114032A EP 0144039 B1 EP0144039 B1 EP 0144039B1
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EP
European Patent Office
Prior art keywords
foamed particles
preliminarily foamed
peak
temperature
preliminarily
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP84114032A
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German (de)
English (en)
French (fr)
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EP0144039A3 (en
EP0144039A2 (en
Inventor
Hideki Kuwabara
Yoshimi Sudo
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JSP Corp
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JSP Corp
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Application filed by JSP Corp filed Critical JSP Corp
Publication of EP0144039A2 publication Critical patent/EP0144039A2/en
Publication of EP0144039A3 publication Critical patent/EP0144039A3/en
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Publication of EP0144039B1 publication Critical patent/EP0144039B1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/228—Forming foamed products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/16—Ethene-propene or ethene-propene-diene copolymers

Definitions

  • This invention relates to preliminarily foamed particles of a non-crosslinked polypropylene-type resin.
  • Bead-foamed molded articles obtained by filling preliminarily foamed particles in a mold and foaming them under heat (to be referred to hereinbelow sometimes as an "in-mold article” or simply a “molded article") have excellent cushioning properties and heat insulating properties and have been widely used as cushioning materials, packaging materials, heat insulating materials, building materials, etc. The demand for these molded articles has ever been increasing in recent years.
  • the present inventors noted the excellent properties of polypropylene-type resins, and have made investigations on in-mold articles from preliminarily foamed particles of non-crosslinked polypropylene-type resins in order to overcome the defects of conventional in-mold articles.
  • the preliminarily foamed particles of non-crosslinked polypropylene-type resins sometimes give in-mold articles having a low density (high expansion ratio), a low water absorption and excellent dimensional stability with a low shrinkage, but sometimes only give products having a high shrinkage. Thus, they do not stably and consistently give in-mold articles of good quality. Furthermore, even in-mold articles of good quality do not have entirely satisfactory suppleness and impact strength.
  • conventional foamed particles of non-crosslinked polypropylene-type resins require high temperatures for their molding, and moreover, the molding is not easy. Accordingly, there is still room for improvement on the molding of the preliminary foamed particles of non-crosslinked polypropylene-type resins.
  • the present invention provides preliminarily foamed particles of a non-crosslinked polypropylene resin based on said alpha-olefin/propylene random copolymer having an amount of the heat of crystallization in the range of 20.9 to 62.8 J/g (5 to 15 cal/g), said preliminarily foamed particles having such a crystal structure that when a DSC curve is drawn by heating 1 to 3 mg of the preliminarily foamed particles to 220°C at a rate of 10°C/min by means of a differential scanning calorimeter, a high temperature peak is observed at a higher temperature than the temperature of the peak inherent to the base resin.
  • the preliminarily foamed particles of a non-crosslinked polypropylene-type resin of this invention is derived from a non-crosslinked 1-butene, 1-pentene and/or 1-hexene/propylene random copolymer having an amount of the heat of crystallization, determined by differential scanning calorimetry, of 20.9 to 62.8 J/g (5 to 15 cal/g) as a base resin.
  • the amount of the heat of crystallization is the heat generation energy which is required for the crystallization of an alpha-olefin/propylene random copolymer in the molten state and measured when about 6 to 8 mg of the random copolymer is heated from room temperature to 220°C at a rate of 10°C/min by using a differential scanning calorimeter and then cooled to about 50°C at a rate of 10°C/ min.
  • the amount of the heat of crystallization can be obtained from the area of a portion surrounded by a straight line 1 connecting points a and b and a peak 2 in the DSC curve shown in Figure 1 (the hatched portion in Figure 1).
  • the amount of the heat of crystallization of the said alpha-olefin/propylene random copolymer exceeds 62.8 J/g (15 cal/g)
  • the preliminarily foamed particles of the random copolymer as a base resin has poor low temperature moldability, and the finally obtained in-mold article has reduced suppleness and impact strength.
  • the in-mold arfticle undesirably shows great dimensional changes upon heating.
  • alpha-olefin constituting the base resin of the preliminarily foamed particles of this invention
  • 1-butene, 1-pentene and/or 1-hexene, 1-butene is preferred.
  • the said alpha-olefin/propylene random copolymer is preferably produced by copolymerizing the alpha-olefin with propylene by using a titanium-containing polymerization catalyst, a vanadium-containing polymerization catalyst. Random copolymers produced by using the vanadium-containing polymerization catalyst are preferred because their preliminarily foamed particles have better moldability at low temperatures.
  • the said alpha-olefin/propylene random copolymer used in this invention preferably contains not more than 50 mole% of the 1-butene, 1-pentene and/or 1-hexene component.
  • the proportion of the 1-butene component is preferably 15 to 40 mole% in order for the copolymer to have an amount of the heat of crystallization of 20.9 to 62.8 J/g (5 to 15 cal/g).
  • the preliminarily foamed particles of this invention are obtained by foaming the said alpha-olefin/ propylene random copolymer as a base resin, and have a crystal structure characterized by the fact that when a DSC curve of the copolymer is drawn on the basis of differential scanning calorimetry, a high temperature peak appears at a higher temperature than the temperature of the peak inherent to the base resin.
  • the DSC curve is obtained when 1 to 3 mg of the preliminarily foamed particles of the polypropylene-type resin are heated to 220°C at a rate of 10°C/min by a differential scanning calorimeter.
  • the high temperature peak in the DSC curve can be distinguished from the inherent peak by the following method.
  • a DSC curve obtained when the sample is heated from room temperature to 220°C at a rate of 10°C is designated a first DSC curve.
  • a DSC curve obtained when the sample is cooled from 220°C to about 40°C at a rate of 10°C/min and again heated to 220°C at a rate of 10°C/min is designated a second DSC curve.
  • the peak inherent to the polypropylene-type resin as a base resin is due to endotherm during the melting of the polypropylene-type resin, and generally appears both in the first DSC curve and the second DSC curve.
  • the inherent peak temperature may slightly differ between the first DSC curve and the second DSC curve, but the difference is less than 5°C, usually less than 3°C.
  • the high temperature peak as referred to in the present invention is an endothermic peak which appears on the high temperature side of the inherent peak in the first DSC curve.
  • Preliminarily foamed particles of the non-crosslinked polypropylene-type resin which do not show this high temperature peak in their DSC curve have poor moldability in a mold and cannot give molded articles of good quality.
  • the high temperature peak is presumably due to the presence of a crystal structure which differs from the structure attributed to the above inherent peak.
  • the high temperature peak appears in the first DSC curve, but does not appear in the second DSC curve obtained by heating the sample under the same conditions. Accordingly, the structure attributed to the high temperature peak is possessed by the preliminarily foamed particles of the polypropylene-type resin of this invention.
  • the difference is desirably at least 5°C, preferably at least 10°C.
  • the preliminarily foamed particles of the non-crosslinked polypropylene-type resin of this invention can be produced, for example, by a process which comprises charging a closed vessel with 100 parts by weight of particles of a polypropylene-type resin (for example, particles of said alpha-olefin/propylene resin), 100 to 400 parts by weight of water, 5 to 30 parts by weight of a volatile blowing agent such as dichlorodifluoromethane, and 0.1 to 3 parts by weight of a dispersing agent such as finely divided aluminum oxide, heating the mixture to a temperature of from Tm-25°C to Tm-5°C (in which Tm is the temperature at which the melting of the resin particles ends) without heating it above Tm, opening one end of the vessel, releasing the resin particles and water into an atmosphere at a lower pressure than the inside of the vessel, and thus preliminarily foaming the resin particles.
  • a process which comprises charging a closed vessel with 100 parts by weight of particles of a polypropylene-type
  • Tm is determined as follows:
  • a sample (6 to 8 mg) is heated to 220°C at a rate of 10°C/min, then cooled to about 40°C at a rate of 10°C/min, and again heated to 220°C at a rate of 10°C/min.
  • Tm the point where the bottom line of the endothermic peak meets the base line.
  • the preliminarily foamed particles of the polypropylene-type resin showing a high temperature peak in the DSC curve can be obtained by not heating the particles above the melting termination temperature Tm in preliminary foaming but restricting the foaming temperature to the above- specified temperature range. If the foaming temperature falls outside the above range, or if it is within the above range but has once been raised above Tm, only the inherent peak appears in the DSC curve of the preliminarily foamed particles, and no high temperature peak appears.
  • the preliminarily foamed particles of this invention are used alone as a material for fabrication in a mold. But as required, they may be mixed in a suitable proporation with conventional preliminarily foamed particles of polypropylene-type resins, and the mixture is used as a material for fabrication in a mold. In other words, the preliminarily foamed particles of the invention may also be used as a modifier for in-mold articles from conventional preliminarily foamed particles of polypropylene-type resins.
  • the preliminarily foamed particles of polypropylene-type resins of this invention are characterized by the fact that (1) said alpha-olefin/propylene random copolymer having an amount of the heat of crystallization, measured by differential scanning calorimetry, of 20.9 to 62.8 J/g (5 to 15 cal/g) is used as a base resin for the preliminarily foamed particles and (2) the preliminarily foamed particles have such a crystal structure that in the DSC curve, a high temperature peak appears on the higher temperature side of the inherent peak of the base resin.
  • the preliminarily foamed particles of the polypropylene-type resin of this invention have better moldability at low temperatures than conventional preliminarily foamed particles of polypropylene-type resins and even when molded at low temperatures, easily give molded articles of a low density (a high expansion ratio). Furthermore, the preliminarily foamed particles of this invention can give in-mold articles having lower shrinkage and water absorption and higher suppleness and impact strength than those obtained from the conventional preliminarily foamed particles of polypropylene-type resins.
  • the mixture can be molded easily at lower temperatures than the conventional preliminarily foamed particles alone.
  • an in-mold article having suppleness intermediate between that of an in-mold article produced from the preliminarily foamed particles of the invention alone and that of an in-mold article produced from the conventional preliminarily foamed particles of polypropylene-type resin alone.
  • a 5-liter autoclave was charged with 3000 g of water, 1000 g of particles of each of the copolymers (base resins) indicated in Table 1, 3 g of ultrafine aluminum oxide (dispersant) and 160 g of dichlorodifluoromethane as a blowing agent, and they were heated with stirring. After the mixture attained the maximum temperature shown in Table 1, it was maintained at the foaming temperature indicated in Table 1. Then, while the inside pressure of the autoclave was maintained at 29.4 bar gauge (30 kg/cm 2 (G)) by a nitrogen gas, one end of the autoclave was opened, and the copolymer particles and water were simultaneously released into an outer atmosphere under atmospheric pressure to foam the copolymer particles. Thus, preliminarily foamed particles were obtained. The apparent expansion ratio of the resulting preliminarily foamed particles is shown in Table 1.
  • the resulting preliminarily foamed particles were subjected to differential scanning calorimetry by using a differential scanning calorimeter by heating them to 220°C at a rate of 10°C/min, and a first DSC curve of the preliminarily foamed particles was drawn. Then, the particles were cooled to 50°C at a rate of 10°C/min, and again heated to 220°C at a rate of 10°C/min by the same differential scanning calorimetry and a second DSC curve was obtained. The presence or absence of a high temperature peak in these DSC curves was observed.
  • the DSC curves of the preliminarily foamed particles obtained in Example 1 are shown in Figure 2, and the DSC curves of the preliminarily foamed particles obtained in Comparative Example 3 are shown in Figure 3.
  • the solid lines show the first DSC curves; the dotted lines, the second DSC curves; 3,3', the inherent peak; and 4, the high temperature peak.
  • the preliminarily foamed particles were pressurized with air under 2.9 bar gauge (3 kg/cm 2 (G)) to apply an internal pressure of 1.4 bar gauge (1.5 kg/cm 2 (G)), and then filled in a mold for a flat plate (with an inside size of 50 mm x 300 mm x 300 mm), and heated by steam to form an in-mold article.
  • the lowest vapor pressure at which molding was possible is shown in Table 1.
  • the resulting in-mold article was dried in an oven at 60°C for 24 hours, and then cooled to room temperature. The various properties of the molded article were measured. The results are also shown in Table 1.
  • the preliminarily foamed particles obtained in each of Examples 1 to 4 were mixed with the preliminarily foamed particles obtained in Comparative Example 4 in each of the ratios shown in Figures 2 and 3.
  • the mixture was filled in the same mold as used in the preceding examples, and heated by steam to form an in-mold article. The lowest vapor pressure at which molding was possible was determined.
  • the in-mold article was dried in an oven at 60°C for 24 hours, and its various properties were measured. The results are also shown in Tables 2 and 3.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
EP84114032A 1983-11-21 1984-11-20 Preminarily foamed particles of non-crosslinked polypropylenetype resin Expired EP0144039B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP58219134A JPS60110734A (ja) 1983-11-21 1983-11-21 無架橋ポリプロピレン系樹脂予備発泡粒子
JP219134/83 1983-11-21

Publications (3)

Publication Number Publication Date
EP0144039A2 EP0144039A2 (en) 1985-06-12
EP0144039A3 EP0144039A3 (en) 1985-12-11
EP0144039B1 true EP0144039B1 (en) 1989-04-19

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ID=16730760

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84114032A Expired EP0144039B1 (en) 1983-11-21 1984-11-20 Preminarily foamed particles of non-crosslinked polypropylenetype resin

Country Status (5)

Country Link
US (1) US4587270A (enrdf_load_stackoverflow)
EP (1) EP0144039B1 (enrdf_load_stackoverflow)
JP (1) JPS60110734A (enrdf_load_stackoverflow)
CA (1) CA1219999A (enrdf_load_stackoverflow)
DE (1) DE3477796D1 (enrdf_load_stackoverflow)

Families Citing this family (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0123144B1 (en) * 1983-03-25 1987-10-07 Japan Styrene Paper Corporation Polypropylene resin prefoamed particles
JPH066637B2 (ja) * 1984-09-03 1994-01-26 住友化学工業株式会社 プロピレン系樹脂発泡粒子
JPS61215631A (ja) * 1985-03-20 1986-09-25 Japan Styrene Paper Co Ltd 型内成型に使用する無架橋予備発泡粒子製造用プロピレン系ランダム共重合体樹脂粒子の製造方法
US4778829A (en) * 1985-07-12 1988-10-18 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Process for preparing pre-expanded particles of thermoplastic resin
JPH0649795B2 (ja) * 1985-11-29 1994-06-29 日本スチレンペ−パ−株式会社 ポリプロピレン系樹脂予備発泡粒子成型体の製造方法
JPH0660255B2 (ja) * 1986-09-16 1994-08-10 三井石油化学工業株式会社 無架橋発泡体
US5026736A (en) * 1987-02-24 1991-06-25 Astro-Valcour, Inc. Moldable shrunken thermoplastic polymer foam beads
JPH07116309B2 (ja) * 1987-02-28 1995-12-13 三井石油化学工業株式会社 無架橋発泡体用組成物
JPH0739501B2 (ja) * 1987-06-23 1995-05-01 日本スチレンペ−パ−株式会社 無架橋直鎖状低密度ポリエチレン予備発泡粒子
US4908393A (en) * 1988-03-24 1990-03-13 Mitsubishi Yuka Badische Co., Ltd. Propylene resin foamed particles and foamed mold article
DE4420590A1 (de) * 1994-06-13 1995-12-14 Basf Ag Polyolefin-Partikelschaum
US5679450A (en) * 1994-07-15 1997-10-21 Jsp Corporation Expanded polyolefin body having thermosetting resin layer directly bonded thereto
DE4436980A1 (de) * 1994-10-15 1996-04-18 Basf Ag Durch Extrusion hergestellte, vorgeschäumte Polyolefinteilchen
JPH08277340A (ja) * 1995-04-05 1996-10-22 Jsp Corp ポリプロピレン単独重合体発泡粒子、及び発泡粒子成型体
EP0918066B1 (en) 1996-08-12 2004-02-18 JSP Corporation Shock absorbing material
KR100341651B1 (ko) * 1996-12-13 2002-11-23 가부시키가이샤 제이에스피 폴리올레핀계수지발포입자및그제조방법
US20020182399A1 (en) 1997-04-01 2002-12-05 Hisao Tokoro Molded body of thermoplastic resin having sound absorption characteristics
TW369475B (en) 1997-06-18 1999-09-11 Jsp Corp Production apparatus of expansion-molded article, auxiliary member for transfer of foamed particles and production method of expansion-molded article
EP1036814B1 (en) 1997-12-01 2004-10-27 JSP Corporation Expanded polypropylene resin beads and a molded article
JP3692760B2 (ja) * 1998-01-30 2005-09-07 株式会社カネカ ポリプロピレン系樹脂型内発泡成形体の製造方法
SG77671A1 (en) * 1998-03-23 2001-01-16 Jsp Corp Foamed and expanded beads of polypropylene resin for molding
EP0963827B1 (en) * 1998-06-11 2002-10-23 Jsp Corporation Molded article of foamed and expanded beads of propylene resin
JP3950557B2 (ja) 1998-07-30 2007-08-01 株式会社カネカ ポリプロピレン系樹脂予備発泡粒子およびそれからの型内発泡成形体の製造方法
KR20020055589A (ko) 1999-12-28 2002-07-09 다케다 마사토시 발포성 폴리스티렌계 수지입자 및 이를 이용한 발포체
US6402434B1 (en) 2000-07-26 2002-06-11 Illinois Tool Works, Inc. Method of applying chemical anchoring adhesive
US6291555B1 (en) 2000-07-26 2001-09-18 Illinois Tool Works Inc Highly viscous chemical anchoring adhesive
US6420458B1 (en) 2000-07-26 2002-07-16 Illinois Tool Works, Inc. Solid amine-cured anchoring adhesive
US6403678B1 (en) 2000-07-26 2002-06-11 Illinois Tool Works, Inc. Rope of chemical anchoring adhesive
US7226650B2 (en) 2004-07-01 2007-06-05 Illinois Tool Works Inc. Wrapped highly viscous chemical anchoring adhesive
US8517641B2 (en) 2009-07-21 2013-08-27 Illinois Tool Works Inc. Anchoring adhesive combination and integrated method of applying it

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0123144A1 (en) * 1983-03-25 1984-10-31 Japan Styrene Paper Corporation Polypropylene resin prefoamed particles
EP0147690A2 (en) * 1983-12-07 1985-07-10 Japan Styrene Paper Corporation Preliminarily foamed particles of non-crosslinked polypropylene type resin

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JPS5923731B2 (ja) * 1980-11-22 1984-06-04 日本スチレンペ−パ−株式会社 ポリプロピレン系樹脂予備発泡粒子
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JPS5943491B2 (ja) * 1981-08-05 1984-10-22 日本スチレンペ−パ−株式会社 ポリプロピレン系樹脂発泡成型体
JPS5855231A (ja) * 1981-09-28 1983-04-01 Japan Styrene Paper Co Ltd ポリオレフイン系樹脂予備発泡粒子の製造方法
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US4504601A (en) * 1982-10-01 1985-03-12 Japan Styrene Paper Corporation Process for producing pre-foamed particles of polypropylene resin
US4464484A (en) * 1982-12-20 1984-08-07 Japan Styrene Paper Corporation Process for producing prefoamed polymer particles

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0123144A1 (en) * 1983-03-25 1984-10-31 Japan Styrene Paper Corporation Polypropylene resin prefoamed particles
EP0147690A2 (en) * 1983-12-07 1985-07-10 Japan Styrene Paper Corporation Preliminarily foamed particles of non-crosslinked polypropylene type resin

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
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Also Published As

Publication number Publication date
CA1219999A (en) 1987-03-31
EP0144039A3 (en) 1985-12-11
JPH0417978B2 (enrdf_load_stackoverflow) 1992-03-26
JPS60110734A (ja) 1985-06-17
DE3477796D1 (en) 1989-05-24
US4587270A (en) 1986-05-06
EP0144039A2 (en) 1985-06-12

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